Polythiocarbonate

The reaction of thiophosgene with various bisphenols using phase-transfer catalysis gives polythiocarbonates (44) ... 

Carbon disulfide yielded oligomeric polythiocarbonates by copolymerization with episulfides252). 

Polythiocarbamates, 23 735-738 Polythiocarbonates, 23 626, 725-729 thermal stability of, 23 726-727 Polythioesters, 23 729-732 preparation of, 23 730-731 Polythioether-based urethane sealants, 22 36... 

Polythiocarbonate urethanes, (I), prepared by Watanabe et aL (1) having molecular weights 2500 Da had favorable refractive indexes and Abbe numbers and were used in plastic lenses. 

TABLE 2. Physical Properties of Poly(thiocarbonate-co-thiourethane) Step 2 Derivatives Prepared by Condensing 2,4-Tolylene Diisocyanate with Step 1 Polythiocarbonates Described in Table 1 Prepared According to the Current Invention... 

Additional polythiocarbonate poly thiol derivatives of the current invention were prepared by the authors (1) and are described. 

The dipole moments of three asymmetric polythiocarbonates derived from bisphenol A are determined in benzene solution at 298 K. Good agreement between theoretical and experimental results can be obtained assuming that the direction of the dipole moment of the thiocarbonate group Is opposite to that in carbonate residues. 

Polymers from Carbon Dioxide Polycarbonates, Polythiocarbonates, and Polyurethanes... 

To address this concern, several organic and inorganic reagents were evaluated as precipitants for heavy metals in a 10-34-0 (N-P2O5-K2O) fluid fertilizer and WPA. Trisodium trithiocyanuric acid (TMT-15), sodium polythiocarbonate (Thio-Red II), and sodium trithiocarbonate (5% Na2 CS3) precipitated arsenic, cadmium, copper, mercury, lead, and zinc from 10-34-0. Ammonium cyanurate was ineffective in removing cadmium from 10-34-0. Thio-Red II and 5% Na2CS3 precipitated mercury, lead, cadmium, copper, and chromium from WPA. A water-insoluble starch xanthate adsorbed mercury, copper, and lead from 10-34-0 and WPA. Sodium sulfide, sodium polysulfide, and potassium ferrocyanide were tested as inorganic precipitants. The polysulfide was twice as effective as the sulfide alone, and concentrations of less than 10 ppm of arsenic, cadmium, mercury, and lead were achieved in 10-34-0. Ferrocyanide reduced the concentrations of cadmium and nickel to less than 10 ppm in WPA. 

Sodium Polythiocarbonate Solution (Thio-Red II). The analytical results from the precipitation tests conducted with Thio-Red II (Table II) show that when one equivalent of Thio-Red II was added for each equivalent of heavy metal present in the 10-34-0, only copper (>96%) and mercury (>95%) precipitated. Furthermore, only small amounts of lead (22%), arsenic (16%), and cadmium (9%) precipitated, while the levels of zinc (<7%), chromium (<1%), and manganese (<1%) in the 10-34-0 were essentially unaffected by addition of Thio-Red II. When a 50% excess of Thio-Red II was used, the amount of lead which precipitated increased to 83%, while the amounts of arsenic and cadmium which precipitated slightly increased to 34 and 36%, respectively. 

Tagle, L. H, F. R. Diaz, and R. Fuenzalida, Polymerization hy Phase Transfer Catalysis. 18. Polycarbonates and Polythiocarbonates from Chlorinated Diphenols, J. M. S.-Pure Appl. Chem, A31, 283 (1994). 

Tagle, L. H., Vega, J. C., Diaz, F. R., Radic, D., Gargallo, L. and Valenzuela, P. (2000) Polymerization by phase transfer catalysis. 25. Synthesis of polycarbonates and polythiocarbonates derived from diphenols containing germanium and silicon in the main chain, J. Macromol. Sci., PureAppl. Chem. 37, 997-1008. 

In general, polythiocarbonates are polymers containing the structural imits (68) with one to three sulfur atoms and unit (69). They are mainly prepared by ROP of the corresponding cyclic monomers, eg, ethylenethiocarbonate (1,3-dioxolan-2-thione) [20628-59-5] or l,3-oxathiolane-2-thione, or by condensation reactions involving dithiols and adequate difunctional coupling compounds. The synthesis and properties of many kinds of polythiocarbonates were reviewed in 1992 (3). 

The synthesis of related poly(ester-thiocarbonate)s containing the ester group in the main chain (218,219) and in the side chain (220) as well as poly(amide-thiocarbonate)s containing the amide group in both the main (221) and side (222) chains under phase-transfer conditions have also been reported. It has been shown that this technique can be effective to prepare polythiocarbonates derived from diphenols containing Si or Ge, bis(4-hydroxyphenyl)-dimethyl-germane, bis(4-hydroxyphenyl)-diphenyl-germane, bis(4-hydroxyphenyl)-dimethyl-silane, and bis(4-hydroxyphenyl)-diphenyl-silane (223). 

Thermogravimetric (TG) investigations exhibited that the thermal stability of this family of polythiocarbonates is in general lower than that of corresponding polycarbonates (224-226). The solution properties (dipole moment and partial specific volume) and chain flexibility of different poljmiers have been studied (227-233). 

Polycarbonates and polythiocarbonates from phosgene and thiophosgene, respectively, have been prepared from diphenols with chlorinated aromatic side groups under phase-transfer conditions using several quaternary ammonium and phos-phonium salts and dichloromethane as solvent. The effed of varying the catalyst and of the strudure of the diphenol was studied [296]. 

Darensbourg DJ, Andreatta JR, Mtuicada AI (2010) Polymers from carbon dioxide polyucarbonates, polythiocarbonates and polyurethanes. In Aresta M (ed) CO2 as chemical feedstock. Wiley-VCH, Weinheim, p 213... 

Table 1. Partial specific volume of polythiocarbonate-bisphenol-A.

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